Karl thiess



Patented Oct. 11, 1932 UNITED srrss KARL THIEss, E IERANKFOR'I -ONJHE-MAIN-SINDLINGEN, AND FRITZ MANNoIaEN, 0E

E ANKEo T-oN-THE-MAr1\T-HooHsT, GERMANY, assrenons 'ro GENERAL ANILINE' WORKS,"ING., on NEW YORK, N. A ooEEonArron on DELAWARE r SULPHUR CONTAINING- VAT .n Es'rUEEs' AND PROCESS OF MAKING :THEM

tNo Drawing. Application filed January 8, 1930, Serial No.*419,450,'and in Germany January 31, 1929.

The present invention relates to'sulphur containing vat dyestuffs anda process of preparing them.

We have found that very valuable and i '5] fast dyestuifs of great tinctorial power and various tints are obtainable by transforming 2.5 diarylamino 3 mercapto 1.4-benzoquinones into the correspondingwthiazine derivatives by? subjecting them to an oxidation process. When using 2.5-dianilido-3-mercapto-lA-benzoquinone, for instance, the reac tion takes the following course starting materials are obtainable, for instance, by causing a 3-halogen-2.5-diarylam- 2 sulphide in the presence of a diluent.

The oxidation of the mercapto compounds can be carried out by'means of various oxidizing agents such, for instance, as air, nitrobenzene, sulphur or the like, it being not a, necessary in many cases to'isolate the mercapto compounds.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto, the parts being by Weight:

(1) A mixture of 15 parts.of 2. 5-dianilido- I 3-mercapto-1Arbenzoquinone of the follow ing formula:

during one hour up to the boiling point and I boiling is continued for 15 minutes.

tallizes out; it is filtered and'washed with The mercapto compounds to be used as 2.5-'dianilido-3-mercapto 1Let-bennoquinone, used as starting material, is a greenishryellow body which dissolves in concentrated sulinmL-benzoquinone to react with sodium 'naphthylamino-3-chloro1.4-benZ0quinone of the formula: I 7 I (I) NH Cl (prepared from 2.6-dichloro quinone and B- naphthylamine) and 300 parts of alcohol, the

Wholeis boiled for 5 minutes and a conceni trated, aqueous solution of 15 parts of sodium n sulphide,(crystallized) and5. parts of sul I phur is added. After having boiled the mix- On cooling the mixture, the dyestuif crys-:

violet-brown dyestufi which has the following formula dissolves in concentratedsulphuric acid to a bluish violet solution and'dyes wool froma light-yellow vat violetbrown shades."

chloro-o-methyl-l.4-benzoquinone of the 01;

lo'wing formula (prepared from 2.3.5-trichloro-6-methyl-L4- benzoquinoner' and paraechloroaniline) are suspended in 300 parts of alcohol the mixture is heated to boiling and a solution of 20 parts of sodium sulphide (crystallized) in 20 parts of water is added. After 5 minutes the hot solution is filtered into dilute hydrochloric V acid, the mercaptan which hasprecipitated is filtered and washed with water. The merc'apa tan which is a brownish yellow body and dis* solves in concentrated sulphuric acid to a blue solution is dissolved in 300 parts of alcoholand subsequently heated to boiling: {Air V is introduced until no more dyestufi precipitates.

Thev dyestufi' is finally filtered and: washed with alcohol and I water;

following formula J anolive brown body which dissolvesin concentrated sulphuric acid to a violetsolution and dyes wool from a light'yellow vat olive brown shades; o. l/Veclainr;

1. As a new product followingformulai 77 v d NH: i

it i

thegfdyestufi of the brown shades. V

has the 7 tion to V 6. J substance of the 'following general structure:

As a new product, the following formula:: v

. p p v a 0 the saiddyestufi-be ing a violet-brown body dissolving in concentrated sulphuric acid vto a bluish violet'solution dyeing; W901i from a light-yellow vat violet brown shades.

- 3. As a new productithe.dyestuff of: the

followingformula: V 7

, amm 'i the said dyestuffibeingtanolive brown body dissolving in concentrated sulphuric .acid to v a: violet solution dyein wool from .aa light- :5 yellow vat -olive brown shades.';=

4. As 'newproducts; sulphur; containing vatidyestufis of the following generalstructure V I V I loo wherein" for a benzene or naphthalene mums and X for hydrogen or, in case of B being a benlzene' nucleus for methyl or hyd en- I Q 5 As"newproducts, sulphur;containing vat dyestuffs of the following formula:

a p V i i I wherein stands for a phenyl group which may contain" chlorine atom -in-pa1"a-posithe 'NH-group, or a'naphthylrgroup and X stands forhydrogen or, in case of B being a phenyl group, for methyl or hydrog n- The process whichcomprises treating a whereiniR stands for a benz ene or naphthalne nilcl'eli 5nd X for hydrogen O1", in case bf B being a, benzene nucleus, for methyl or hydrogen with anoxidizing agent.

In testimony wh'ereof, we afiix our signaturs; I

KARL THIESS. FRITZ MKNNCHEN. 

